Stereoselective synthesis of (1R,3R,5S-1,3-dimethyl-2,9-dioxabicyclo[3.3.1]nonane

(1$\text{R}$,3$\text{R}$,5$\text{S}$)-1,3-Dimethyl]-2,9-dioxabicyclo[3.3.1]nonane $\text{1}$ has been stereoselectively synthesized based on a highly stereoselective method for the synthesis of 1,3-$\text{syn}$-polyol.     

pH-dependence of 31P-NMR spectroscopic parameters of monofluorophosphate,phosphate, hypophosphate,phosphonate, phosphinate and their dimers and trimers

³¹P-NMR chemical shifts and coupling constants of nine inorganic phosphorus compounds composed of different structural units or oxidation numbers P^V, P^IV, P^III, and P^I were measured in the pH-range 3 ～ 11. A concise map of NMR data providing the pH-dependence of the chemical shift (δ-pH map) was set up to be used for identifying phosphorus compounds under varying pH-conditions. Chemical shifts of monofluorophosphate, as well as most phosphorus compounds of oxidation numbers 5 and 4, were greatly dependent on pH, in contrast to the less or negligible pH-dependence of phosphorus compounds of oxidation numbers 1 and 3. Monofluorophosphate gave the parameters: δ=+1.3±0.2 ppm and ¹J_PF=870±0.2 Hz, that remained unchanged at pH>6, but varied at pH<6. The practical use of the δ-pH map was shown with a few kinetic experiments in which monofluorophosphate was enzymatically hydrolyzed by alkaline phosphatase (EC3.1.3.1) at pH 7.2 and non-enzymatically at pH 3.     

Inhibition of the formation and decay of stilbene core radical cations by the dendron during the photoinduced electron transfer

Formation and decay processes of stilbene core radical cation (ST*+) during the photoinduced electron transfer have been studied for a series of stilbene bearing benzyl ether-type dendrons (D). ST*+ and the radical cation of peripheral dendron (D*+) were generated by intermolecular hole transfer from biphenyl radical cation, which was generated from photoinduced electron transfer from biphenyl to the singlet-excited 9,10-dicyanoanthracene in a mixture of acetonitrile and 1,2-dichloroethane (3:1). An intramolecular dimer radical cation of benzyl groups at the terminal of stilbene dendrimer was indicated as a hole trapping site. Subsequent hole transfer from the trapping site to the core ST generated ST*+. The shielding effects of D depending on the dendrimer generation on the growth and decay of ST*+ were observed. It was revealed for the first time that D acts as the hole trapping site and the hole conductor on the way of the exothermic hole transfer from the terminal of D to the central core ST. We also found that D inhibits the charge recombination with 9,10-dicyanoanthracene radical anion because of the steric hindrance.     

Efficient emission from charge recombination during the pulse radiolysis of electrochemical luminescent donor-acceptor molecules with an ethynyl linkage

Efficient monomer and excimer emission from various donor-acceptor substituted phenylethynes (PE), which are known as efficient electrogenerated chemiluminescent molecules, was observed with time-resolved fluorescence measurement during the pulse radiolysis in benzene. On the basis of the transient absorption and emission measurements, and steady-state measurements, the formation of PE in the singlet excited state (1PE*) and the excimer (1PE2*) can be interpreted by the charge recombination between the PE radical cation (PE.+) and the PE radical anion (PE.-) which are generated initially from the radiolytic reaction in benzene. It is suggested that the positive and negative charges are localized on the donor and acceptor moieties in the radical cation and anion, respectively. This mechanism is reasonably explained by the relationship between the annihilation enthalpy changes (-DeltaH' degrees ) and singlet excitation energies of donor-substituted phenyl(9-acridinyl)ethynes (1(a-e)). In addition to the monomer emission, the compounds bearing weak donors (1(a-d)) show the excimer emission due to a very small twist angle between the donor and acceptor moieties. For the phenyl(9-cyano-10-anthracenyl)ethynes (2(c) and 2(f)), although they also show the monomer and excimer emissions, it cannot be explained by the relationship between -DeltaH' degrees values and their singlet excitation energies, suggesting the formation of the ICT state and H-type excimer in which two 9-cyano-10-anthracenyl moieties are stacked face-to-face with donor bearing a benzene ring projecting perpendicularly away from each other through the charge recombination between 2.+) and 2.-) and/or triplet-triplet annihilation.     

Theoretical analysis of binding specificity of influenza viral hemagglutinin to avian and human receptors based on the fragment molecular orbital method

The hemagglutinin (HA) protein of the influenza virus binds to the host cell receptor in the early stage of viral infection. A change in binding specificity from avian 2-3 to human 2-6 receptor is essential for optimal human-to-human transmission and pandemics. Therefore, it is important to reveal the key factors governing the binding affinity of HA-receptor complex at the molecular level for the understanding and prediction of influenza pandemics. In this work, on the basis of ab initio fragment molecular orbital (FMO) method, we have carried out the interaction energy analysis of HA-receptor complexes to quantitatively elucidate the binding specificity of HAs to avian and human receptors. To discuss the binding property of influenza HA comprehensively, a number of HAs from human H1, swine H1, avian H3 and avian H5 viruses were analyzed. We performed detailed investigations about the interaction patterns of complexes of various HAs and receptor analogues, and revealed that intra-molecular interactions between conserved residues in HA play an important role for HA-receptor binding. These results may provide a hint to understand the role of conserved acidic residues at the receptor binding site which are destabilized by the electrostatic repulsion with sialic acid. The calculated binding energies and interaction patterns between receptor and HAs are consistent with the binding specificities of each HA and thus explain the receptor binding mechanism. The calculated results in the present analysis have provided a number of viewpoints regarding the models for the HA-receptor binding specificity associated with mutated residues. Examples include the role of Glu190 and Gln226 for the binding specificity of H5 HA. Since H5 HA has not yet been adapted to human receptor and the mechanism of the specificity change is unknown, this result is helpful for the prediction of the change in receptor specificity associated with forthcoming possible pandemics.     

Fine-tuning of radiolysis induced emission by variable substitution of donor-/acceptor-substituted tetrakis(arylethynyl)benzenes

Emission from charge recombination between radical cations and anions of various tetrakis(arylethynyl)benzenes (TAEBs) was measured during pulse radiolysis in benzene (Bz). The formation of TAEB in the excited singlet state ((1)TAEB*) can be attributed to the charge recombination between TAEB (*+) and TAEB (*-), which is initially generated from the radiolytic reaction. It was found that the charge recombination between TAEB (*+) and TAEB (*-) gave (1)TAEB* as the emissive species but not excimers because of the large repulsion between substituents caused by the rotation around C-C single bonds. Since donor-/acceptor-substituted TAEBs possess three types of charge-transfer pathways (linear-conjugated, cross-conjugated, and "bent"-conjugated pathways between the donor and acceptor substituents through the ethynyl linkage), the emission spectra of (1)TAEBs* with intramolecular charge transfer (ICT) character depend on the substitution pattern and the various types of donor and acceptor groups during pulse radiolysis. Through control of the substitution pattern (e.g., the position of the nitrogen atom within the pyridine ring or the number of acceptors per arene ring of the regioisomeric donor-/acceptor-substituted TAEBs with donating N, N-dibutylamino and accepting pyridine unit (N1-9) and those with donating N, N-dibutylamino and accepting one (F1-3), two trifluoromethyl (F4-6), or perfluorinated arene (F7-9) units), fine-tuning of radiolysis induced emission color can be achieved.     

Dynamical suppression of dephasing for Markov processes

It is shown that the dephasing of a qubit caused by a Markov process can be suppressed by a successive application of π-pulses if two-time conditional probability of the stochastic variable depends only on the time-difference. The several types of the π-pulse sequence are compared in the case of the two-state jump Markov process.     

On the Dual Mode of Aldol Cyclization of Bicyclo-[4.3.1] Decane-3,8-Dione: A Novel,Efficient Entry into the Isotwistanone System

Isotwistanones have been highlighted since their use in the sesquiterpene syntheses.¹ Begley and coworkers reported a new access to this system via the postulated aldol cyclization of bicyclo [4.3.1]decane-2, 7-dione.² We have found another novel path of a similar mode.